Manufacture of esters of polymerized carbohydrates



Patented Mar. 19 1935 I if v {OFFICE MANUFACTURE OF ESTERS OF POLY- MERIZED CARBOHYDRATES Max Hagedorn, Dessau in Anhalt, Germany, assignor to I. G; Farbenindustrie Alstiengesellschaft', Frankfort-on-thra-Main, Germany, a

- corporation-of Germany No Drawing, Application February 6, 1929, figigal No. 338,051. In Germany February 10,

1 10*Claimsf, (01. 260- 101) My 'p'rese'nt invention relatesto'the manufacployedjointly a higher fatty acidhalide, for ture"of esters of polymerizedcarbohydrates and ample stearyl chloride or lauryl'chloride, and moreparticularly-toan improvement intheknown any other acid halide, for example the chloride of 5;; process of preparing such esters-by acting wane acetic acid, benzoic acid, naphthenic acid. a

chloride of organic acids of higher molecular While the known processes for making celluweight upon polymerized carbohydratestreated lose esters of higher fattyacids always lead to with a caustic alkali with theeffect-of obtaining more or less strongly colored products, the prod-'- directly esters soluble'in halogenated hydrocaructs obtainable according to the present -inven-- J-i'bonsr Another-advantaged my invention is'that tion arequite colorless. Theseproducts aiesuit-- theinewproductsiobtainable by this process are in able for allethe purposes for 'vvhichhithert'o cararpure',,nearlyicolorless state i bohydrate derivatives have been suggestedq 'Ihe'y The esterificationcfpolymerized carbohydrates are particularly useful for making threads"; arms with: higherfatty acids. has: not hitherto been lacquers, masses which can be spread withakn'ife} g;wachieved'.without preliminary treatment, because coatings on paper or fabric, insulating masses,

ofitheunca'pacity of thesexcarbohydrates to react plastic masses or the like. Theymay be moulded on account oftheir colloidalcharacter. It is only' by" pressure at a raised temperature belowtheir possible to esterify polymerized carbohydrates melting point or may be usedwhen' dissolved in with-higherrfattyaacids-bypreviously causing them an organic solvent. i Vtosswell 'in.strongzaqueous alkali hydroxide solu- ,The new esters or" polymerized carbohydrates tions. Thisf'treatrnent produces-the'known alkali derived from cyclic carboxylic acids, for example compounds of the carbohydrateszwhich, in aconcyclopentane-carboxylic acid and cyclohexaneditionz moistiwith:watenjcan-react withfatty'acid carboxylic'acid, are colorless and dissolve comhalid i i I pletelyinaroinatic hydrocarbons, in chlorinated -Eonrswelling3the carbohydrates strong. alkali. hydrocarbons and in fatty'acid esters.- In ether lyes containing per cent. and more. of alkali and in aliphatic hydrocarbons theyswell stronghydroxide: are necessary,sincelonly'in this case 1y. These solubilities vary, if, besides'the radicle alkali, compounds ofthe carbohydrates are of the'cyolic carboxylic acid, stillother acid-radi formed-wwhich react, easily; Such treatment cles are introduced, and, furthermore, the solubilleads; in the; case of cellulose, to the: compound ities vary according to the changes in the ratios, 7 30 (CeI-hoOsJaNaOH; and with the nature of the said other radicles in- When: the alkali compounds of the carbohy-; troduced. i v drates; asrhasbeenproposed for alkalicellulose; Thecarbohydrate compounds which. contain are esterified withacidhalidein the, usual man,- radicles of cyclohexane -carboxylic acids (naphner,;that is tosay; accompanied by c0oling,there I thenic acids) exhibit the remarkable property are obtained insoluble esters-which must be subthat at ordinary temperature they'are very hard mittedtoaseparate and special treatment, since and strong," while at moderate itemperatures they 'acquire properties of solubility onlyby such (about 50 C(and therefore far below their melt further treatment, ing point, which is about 200 (3.), they soften According to the present invention esters Whic and are-capable of being moulded. This'property 40 are, soluble in organicgagents are obtained in ac makesit'possibleto workthemup'without vaddisingleoperation, when-the operationis conducttion of a solvent or softening agent. ed withoutrremoving theheatof reaction evolved, Thefollowing e a p illustrate the invenduring. the'esterification. The reactionmaybe tion: v n

, carried out-with 'the addition'of some, more heat; Examplc1.10 grams of finely powdered rice Fortheesterificationof any polymerizedcar starch are stirred quickly with lO cc. of aqueous bohydratethe-halide of-an acid of ahigher molec sodium hydroxide solution gof 40 per cent. ularweig-ht may be used, that is to say, for instrength. The alkali starch 'thus obtained is stance. ofv any saturatedon unsaturated, substisuspended in cc. of benzene and a mixture of,

--tuted:onunsubstitutediatty acid'containingpmore l6-cc.- of benzoyl chloride and 14 cc. of lauryl 50 than-five carbon atoms'or of an' analog-ous cyclic chloride added. The heat of the reaction, carboxylic acidr V which is soon developed, brings'the benzene to The esterification may-be executed by. the aid' gentle ebullition. The mixture is viscid throughofcam-ixture'of aiattwacidhalide-withanother out and finally solidifies to ajelly. From the,

. organic or inorganic acid halide, mixedesters-thus latter, the sodiumchloridc, produced by there- 5 being formed. For instance, there may be emaction, iswashedvout by means of Water. The

residue insoluble in water consists, after thorough extraction with methanol, of pure, quite colorless starch-laurate-benzoate, which dissolves in dichloro-methane and swells strongly in ben- 5 zenej Solutions of it may easily be filtered off from a small quantity of undissolved particles. Ezwmple 2.--l0 grams of cellulose are treated for 4 hours with an aqueous sodium hydroxide solution of 40 per cent. strength at C., to

10 cause swelling and are then freed from an ex-v cess of alkali lye by pressing until the mass weighs 30 grams. The alkali-cellulose is suspended in 80 cc. of chloro-benzene. There are then added 80 cc. of lauryl chloride; the temperature of the mixture rises within 5 minutes from C. to 7580 C. This temperature is maintained for about 15'minutes. There is produced a cloudy, viscid solution which, after'about 30 minutes solidifies to a jelly. This mass is 20 extracted several times with boiling alcohol and water and then dried. 23 grams of a. snow white cellulose laurate' soluble inbenzene and in chloro-methane are -obtained.-

Example 3,-10 grams of agar-agar, in the 25 form of a powder fine as dust, are stirred with 10 cc. of aqueous caustic soda solution of 40 per cent. strength. Swelling is allowed to continue for 15 minutes, and the mass is then dispersed by strongly shaking ,in 50 cc. of benzene. On

addition of 50 cc. of a mixture of the chlorides of cocoanut oil fatty acids, the suspension is.

converted, with strong evolution of heat, into a thickish jelly. The carbohydrate derivative is precipitated with ethanol and extracted. by

boiling water to. free itfrom the salts soluble in $11 water and fatty acids, which have been formed by the reaction. There is thus obtained a cocoanut oilfattyacid ester of that carbohydrate of agar-agar, which forms the fundamental 0 constituents thereof; the. product is snow white,

clearly soluble in aromatic and in chlorinated aliphatic hydrocarbons.

. Example 4.10 grams of cellulose are softened for 3 hours at -12 C. in an aqueous sodium hydroxide solution of 40 per cent. strength and the alkali cellulose thus produced is freed from the excess of lye by pressingv to a weight of 30 grams.

grams of cellulose, 8 grams of. caustic soda and 12 grams of water, is comminuted and suspended in 80 cc. of chlorobenzene.

which is soluble in aromatic and in chlorinated I aliphatic hydrocarbons. It may be pressed to thin, transparent colorless plates by the process described in application Serial Number 269,294

' filed April 11, 1928.

Example 5.--l0 grams of starch are stirred witha solution of 12 grams of sodium hydroxide in 18 grams of water until a homogeneous gelatin'ous mass has been produced. This mass is "introduced slowly into a mixture of 47 grams of phenyl-acetic acid chloride and 60 cc. of ben-" zene. The heat of reaction evolved heats the mixture up to theboiling point of the benzene. The mixture is allowed to stand for 24 hours, and then The alkali cellulose, composed of 10- There is then added I a mixture of 60 cc. of naphthenic acid chloride percent strength to forman alkali-imetalfcoim.

4 times its weight of methanol are added; the

ester separates from the liquid and is washed four times with methanol and then thoroughly with hot water. This ester contains 70 per cent.

of bound phenyl-acetic acidand dissolves in 5 halogenated hydrocarbons.

As can be seen from the foregoing'examples,

I may introduce into the molecule of the polymerized carbohydrate either an aliphatic acid with more thanfive carbon atoms or a cyclic 1o carboxylic acid with more than five carbon atoms or a mixture of these compounds. In the. following claims the term .organic acid with s more than five carbon atoms is intended to include aliphatic as well as cyclic 15 carboxylic acids.

3 I claim: I

1. The process of manufacturing cellulose naphthenate laurate'which comprisesv swelling cellulose in an aqueous alkali metal hydroxide go solution of at least 30 per cent. strength, acting upon the .wet' alkali metal cellulose simultaneously with lauric acid chloride and naphthenicacid chloride and promoting the reaction by the heat... formed in this esterificationprocess; ng

2. Cellulose naphthenate laurate soluble in aromatic and in chlorinatedaliphatic.hydrocares bons, being of whitev appearance and forming;- when pressed transparentqcolorless .plates 3. The'process of manufacturing, starch-lanai rate-benzoate which comprises producingalkalii starch by mixing finely powdered rice starchwith. an aqueous solution .of sodium. hydroxide 01.40 per cent strength, suspending thefalkali; starch; in a mixture of benzoyl' chloride and .lauryl: 011101; ride in benzene, and promoting the reactionby-f the heat formed in'this esterifying process.

4. The process of manufacturingthe cocoa-nut; oil fatty acid ester of agar-agar whiehcomprises" mixing finely powdered agar-agar .withaque! .140

ous solution of sodium hydroxide of 40 per cent: strength,dispersing thereaction mass bystrongly shaking with benzene, adding .amixture ofthe chlorides of cocoanut oil fatty acids, and'promot.-: ing the reaction by the heat formed inthis esterl 4g fyingprocess. p A 5. The process of .manufacturing anester ot'ea polymerized carbohydrate which comprises swelling the polymerized carbohydrate in an aqiieou's solution of analkali metal hydroxide or at least" 59 30 per cent strength to form an alkali metalco'zn 1 pound, finely distributing said alkali metalbom pound in a solvent for said ester, and acting on said alkali metal compound-with a mixture of halides of acids, selected from the group consist--- '5 ing of aliphatic acidswith more than-5 carbon f" atoms and of benzoic acid without-removal o the heat of reaction formed inthesaidesterify' ing process. 6. The process of of acids, selected fromthe group consisting' of;

aliphatic acids with more than 5'c'arbon atoms and of benzoic acid without removal of the heat f of reaction formed in the said esterifying process; 70

-7. The process of manufacturing an ester o'ta A polymeric carbohydrate which comprises' swellingthe polymerized carbohydratein an aqueous solu tion of an-alkaliimetal hydroxide of at least manufacturing a=cellulose 6Q esterwhich comprises swellingcellulose in pound, finely distributing said alkali metal compound in a solvent for said ester, and acting on said alkali metal compound with a halide of a higher fatty acid with more than five carbon atoms and with a halide of naphthenic acid.

8. The process of manufacturing a cellulose ester which comprises swelling cellulose in an aqueous solution of an alkali metal hydroxide of at least 30 per cent strength to form alkali cellulose, finely distributing said alkali cellulose in a solvent for said cellulose ester, and acting on said alkali cellulose with a halide of a higher fatty acid with more than five carbon atoms and'with a halide of naphthenic acid.

9. The process of manufacturing cellulose laurate naphthenate which comprises producing alkali cellulose by mixing cellulose with an aqueous heat formed in this esterifying process.

10. The process of manufacturing cellulose laurate which comprises producing alkali cellulose by mixing cellulose with an aqueous solution of sodium hydroxide of 40 per cent strength at -10 C., pressing the alkali cellulose formed to three times its original weight, suspending the alkali cellulose in chlorobenzene, adding lauryl chloride, and promoting the reaction by the heat formed'in this esterifying process.

MAX HAGEDORN. 

